Organosilicon polymeric dyes

ABSTRACT

Polymeric dyes prepared by the copolymerization of a diorganodifunctionalsilane with a derivative of anthraquinone containing two aliphatic hydroxy groups. The polymeric dyes are useful as coloring material in photoresist formulations and for other purposes.

Baptista et al .1541 j ORGANOSILICON POLYMERIC DYES [72] Inventors: John L. Baptists; Frederick J. Rauner; John A. Ford, Jr., all of Rochester, NY.

[73] Assignee: Eastman Kodak Company,

' Rochester, NY.

[22] ,Filed: v 7 Aug. 18, 1969 [21] App1.No.: 851,046

[52] 11.8. C1. ..260/37 SB, 8/D1G. 1-, 8/D1G. 7 [51] Int. Cl. .,.C08g 51/04 [58] Field of Search ...260/37 SB; 8/D1G. 1; 8/DIG. 7

[56] i I .Reterences Cited UNITED STATES PATENTS 2,727,045 12/1955 McSheehy ..260/379 2,131,712 9/1938 Schaeller et al. ..260/86 3,025,179 3/1962 Halhein....' ..260/37 SB 2,732,382 f1/1956 .Minsk et a1. ..260/379 2,925,313 2/1960 Bailey et a1. ..8/D1G.' 1 X FOREIGN PATENTS OR APPLICATIONS [451 Oct-1'7, 1972 OTHER PUBLICATIONS American- Chemical Society, Chemical Abstracts,

, paragraphs: 67:3690u (1967).

American Chemical Society, Chemical Abstracts, paragraphs:57:7419i(1957).

American Chemical Society, Chemical Abstracts, I

paragraphs: 68:60525p (1968). Chemical Abstracts, par. 68:60525p (1968).

. and Joshua G. Levitt z [57] ABSTRACT Polymeric dyes prepared by the copolymerization of a diorganodifunctionalsilane with a derivative of anthraquinone containing two aliphatic hydroxy groups. The polymericdyes are useful as coloring material in photoresist formulations and for other purposes.

7 Claims, No Drawings ORGANOSILICON POLYMERIC DYES This invention relates to polymeric dyes and, in particular, to polymeric dyes prepared by the copolymerization of a diorganodifunctionalsilane with a derivative of anthraquinone containing two aliphatic hydroxy groups. 1 v 1 The general type reaction of the condensation 'of a diorganodifunctionalsilane with an aliphatic or aro-, matic diol isknown, for example, from the Journal, of

Applied Polymer Science, Vol. 9, pp. 295-311 (1965). ,The main interest of this earlier work was to develop high molecular weight, thermally stable polymers for .use as coatings, plastics, adhesives, elastomers, etc.

However, this general type condensation reaction has not been used to make polymeric dyes, nor have such dyesjbeen described or used.

In order to be better able to observe the formation of photographic images, for example, photoresist images, during and after development, it is expedient to incor-. porate coloring material into the photosensitive for mu-,

lations. This procedure is particularly useful in positive- I 25,000. The polymeric dyes of this invention are convemently prepared by reacting a diorganodifunctionalsilane having the formula:

working sys'terns'where an image is developed in ex- 1,500 to 25,000 and which are soluble in organic solvents. I

It is still a further object of the invention to provide such polymeric dyes which are. film formers and which have little or no solubility in basic aqueous solutions.

it is another object to provide photoresistcompositions of good color containing such polymeric dyes.

The foregoing and other objects of this invention are,

achieved by; providing adye copolymer of a diorganodifunctionalsilane and an anthraquinone derivative having two aliphatic hydroxy groups; the

copolymer having repeating units of the formula:

' wherein R is hydrogen, hydroxy or halogen; the

copolymer having a molecular weight of from 1,500 to with a derivative of anthraquinone having the formula:

wherein R R and n are the same as above and R is a hydrolyzable or condensation displaceable functional group which, under the reaction conditions, will readily separate from the silane and will combine with the hydrogen atom of analiphatic hydroxy radical, for example, R is a halogen, an anilino', an alkoxy, an alkylamino, or the like groups.

The diorganodifunctionalsilane which is useful to produce polymers according to the invention includes two non-functional groups, R which are not capable ofrcacting with the anthraquinone derivatives. These R groups may be the same or different and are preferably lower alkyl, lower cycloalkyl, or lower aryl, or lower alkenyl, either unsubstituted or substituted with non-interfering groups. The term lower alkyl means straight or branched chain alkyl groups of up to seven carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyland the like, as well as aryl substituted alkyl such as benzyl and the like. The term lower cycloalkyl means groups of four to 10 carbon includes alkyl'substituted cycloalkyl. The term lower aryl means phenylor substituted phenyl of up to carbon atoms such as tolyl and the like. The term lower alkenyl means groups such as vinyl, allyl, and the like from two'to seven carbon atoms. As mentioned above, thesegroups can be substituted with anon-interfering substituent, thatis, a substituent which will, not interfere with the polymerizationreaction, such as hydroxy, alkoxy, and the like.

The silanealso includes two functional groups, R whichenter into he. polymerization reaction with the hydroxy, groupsfof the anthraquinone derivative and which can be the same or different. Suitable functional groups are those which are hydrolyzable or condensation displaceable and hence can react with the hydroxy 4 hydroxy in the case of the anthraquinone derivative and R, in the case of the silane.

The polymeric dyes of this invention are useful in a I variety of applications for which dyes are convengroupof theanthraquinone compound, and include halogen, alkylamino, cycloalkylamino, arylamino, alkoxy andthe like groups including such groupssubstituted with'non-interferingsubstituents. Preferably R is a halogen, an. anili'no, an alkyl-anilino of seven to 10 carbon atom s',.a'n ;alkylamino of one to seven carbon atoms, or a cycloalkylamino of four to 10 carbon atoms. Suitable silanes include diphenyldiethoxysilane, diphenyldichloro'silane, dimethyldianilinosilane, diethyldianilinosilane, di-(p-chlorophenyl)dichlorosilane,. dibenzyldichlo'rosilane, methylphenyldianilinosilane and di-n-propyldichlorosilane.

. The-.anthraquinones include two monovalent functionalghydrogen terminated ethyleneoxyamino groups having the formula.ll+O CH -CH,+,,NH- wherein n is an integer of; l to 4, preferably 1 to'2. The anthraquinones can also include one or two substituents, R which can be the same or different and which will'not condense with the silane, such as a hydroxy, a halogen, a nitro, an alkyl,-an aryl, a cycloaL kyl and the like groups, such as defined above for R Suitable derivatives of. anthraquinone include 1,4-

bis(2-hydroxyethylamino)anthraquinone, l,4-bis[2-(2- hydroxyethoxy)ethylamino]anthraquinone, 1,5-bis(2- hydroxyethylamino )anthraquinone, l ,5 -bis[ 2-( 2- hydroxyethoxy) ethyiamino]-anthraquinone, l,8-bis(2- hydroxyethylamino)anthraquinone, and l,4-bis(2-' hydroxyethylarnino)-5,8-dihydroxyanthraquinone.

Copolymers according to the invention are produced by reacting substantially equimolar amounts of the silane and anthraquinone derivative. The. reaction is preferably performed by a melt polymerizationv technique such as is described in the Journal of Applied Polymer Science," vol. 9, pp. 295-311 (1965). The reaction flask isJheated to a temperature of 150-300 C., and vacuum to about 20 mm or less, preferably 1.0 mm or less, is applied with stirring while the temperature is maintained and the reaction continued until polymerization is complete. The reaction is usually tionally employed. A particularly preferred .use for these polymeric dyes is to impart color'to photoresist compositions and in particular, positive working photoresist. compositions, so as to improve observation of the developed photoresistimage. These dyes are particularly attractive for use in such compositions since they are soluble in the organic solvents normally used in coating such compositions, but are fast to alkali, which may be used in development of the resist image or etching of the substrate on which the photoresist composition is coated. I

These polymeric dyes can be incorporated in *a variety of photoresist compositions. Typical of such compositions are those based on such light-sensitive resin materials as cinnamic acid esters of-hydroxy polymers such as are described in Minsk et al. U.S. Pat. No. 2,690,966, Minsk U.S.-Pat. No. 2,725,372, Robertson et al. vs; Pat. No. 2,732,30l 'and Sorkin u.s. Pat.

No. 3,387,976; cinnarnylidene malonate polyesters such as are described in Michiels et al. U.S.;P-at. No. 2,956,878, and Clement et al. U.S. Pat. No. 3,173,787; azide sensitized rubber compositions such as are described in Hepher et al. U.S. Pat. No. 2,852,379 and Sagura et al. U.S. Pat. No. 2,940,853; polymericquinone diazides such as are described in Rauner et al. U.S. Pat. Application Ser. No. 684,636, filed Nov. 21, 1967, and the like.

The amount of polymericorganosilicon dye incorporated in the photoresist composition can vary depending upon-the particular photoresist composition employed, the depth of color desired, and the like criteria. In general, the dye-can be employed in amount of about from 1 to 10 percent based on the weight of solids in the resist composition.

In addition to the light-sensitive component and the polymeric organosilicon dye, the resistcomposition denda as additional non-light-sensitive polymers to complete in less.than 1 hour and a reaction time of not more than 6 hours is sufficient. Provision is made for the removal of the volatile by-product R H whichboils off under the temperature and pressure conditions present inthe reaction vessel.

The polymer produced has a molecular weight of 1,500 to 25,000 and has a plurality of repeating units having formula-l. Generally, the polymer will comprise from 4 to 50 of these'repeating units and will be terminated by the groups present on the reactants, namely modify the physical properties of the resist,- sensitizers, surfactants, coating aids, and other addenda conventionally employed by, and known to those skilled in the art. The resist composition is coated on conventional substrates, such as metals, glass, polymeric materials,v

and the like, by such techniques as whirl coating, clip coating, etc. v

The following examples are included for a further understanding of the invention.

EXAMPLE 1 l,5-Bis[2-(2-hydroxyethoxy)ethylamino] anthraquinone (14.2 g, 0.0343 mole) and diphenyldianilinosilane (12.6 g, 0.0343 mole) are placed in a 500- ml three-necked flask equipped with a nitrogen inlet, a mechanical stirrer, a vacuum source, and an outlet to a collection flask for the aniline by-product. The system is flushed with nitrogen, and a vacuum applied gradually. The reaction flask is heated to C. A final vacuum of 0.5-4.0 mm of Hg,;heating at 165 C., and stirring are maintained for 1 hour. The polymers number-average molecular weight is 8,200 i 25 percent. A film cast from chloroform appears red in color.

The polymer of this example conforms to structure I wherein n is 2, R is phenyl, Q is as shown in structure Ilb, and R," is hydrogen. Similar results are. obtained when the diphenyldianilinosilane is replaced by an equimolar amount of one of various other diorganodianilinosilanes described by structure Ill, and when the derivative of anthraquinone is replaced by an equimolar amount of the derivative of anthraquinone where ri= 3 or 4;

EXAMPLE2 1,4-Bis[2-(2 -hydroxyethoxy)ethylamino] number-average molecular weight is-3,000 25 peranthraquinone (3.26 g, 0.00789 mole) and diphenyldi- V anilinosilane (2.88 g, 0.00789 mole) are placed in a SOO-mlthree-necked flask equipped with a nitrogen inlet, mechanical stirrer, a vacuum source, and an outlet to a collection flask forthe aniline by-product. The system is'flushed with nitrogen, and a vacuum is apanilinosilanes as described by structure III, and when -the 1,4'or 1,5 or

cent. A film cast from chloroform appears blue in color. The polymer conforms to structure 1 wherein n is 2, R is phenyl, Q is asshown in structure'lla, and R, is

hydrogen. Similar results are obtained when diphenyldichlorosilane is replaced by an equimolar amount of one of various other diorganodichlorosilanes as described by vstructurelll, and when the derivative of anthraquinone is replaced by an equimolar-amount of 1,8 derivative of anthraquinone where n=1 ,2,3,or 4. II

I EXAMPLE '5 1,4 -Bi s( 2-hydroxyethylamino)-5 ,8-dihydroxyanthraquinone(l2.0 g, 0.0335 mole)"and diphenyldichlorosilane (7.65 g, 0.0302 mole)'a're placed in a 500-ml three-necked flaskequipped with a nitrogen inlet, a mechanical stirrer, a vacuum source, and an outlet-to a collection flask. The system is evacuated with a Ywater aspirator, and the reaction flask is gradually the derivative of anthraquinone is replaced by an equimolar amount of the derivative of anthraquinone where n=3 or 4.

' I XAMPL-Es I l,4-Bis(2-hydroxyethylamino)anthraquinone (7.80

'g, 0.0329 mole) and diphenyldianilinosilane (8 .75 g,- 0.0329 mole) are placed in a 500-rnl three-neckedflask 1 equipped with a nitrogen inlet, mechanical stirrer, a vacuum source, and an outlet to a collection-flask for the aniline by' product. The system is flushed with nitrogen, and a vacuum is applied gradually. The reaction flask is heated to 200 C. A final vacuum of 0.5-1.0mm of H g, heating at 200 C., and stirring are maintained for 4 hours. .The polymers number-average molecular-weight isv 2,000 i 'percent. A film cast from chloroform appears blue in color. This polymer I conforms'to structure I wherein n is l, R, is phenyl, Q is as shown 'by structure Ila, and R is hydrogen. Similar results are obtained using various other'diorganodianilinosilanes, for example, dimethyldianilinosilane.

I EXAMPLE 4 1 ,4-Bisl2 (2-l1Ydt0xyethoxy )ethylamino] anthraquinone (34.5 g, 0.0835 mole) and diphenyldichlorosilane (21.1 g, 0.0835 mole) are placed in a 500-ml three-necked flask equipped with'a nitrogen inlet, a mechanical stirrer, a vacuum source, and an outlet to a collection flask. The system is evacuated with a water aspirator, and the reaction flask is gradually heated'to 175 C. over the period of an hour. The vacuum source is switched to a vacuum pump (0.5-1.0v mrn of Hg), and thereaction flask is heated at 175 C. for an additional hour. Stirring is maintained throughout the entire preparation. The polymers heated to 180 C. over the period of an hour. The

vacuum source is switched to.a vacuum pump (0.5-1.0 mm of Hg), and the reaction flask is heated at 180 C. for an additional hour. Stirring is maintained throughout the entire preparation. The polymers number-average molecular weight is estimated to be 2,000-3,000. A film' cast from chloroform-appears blue in color. This polymer conforms to structure I wherein n is 1, R is phenyl, Q is as shown in structure Ila, and R is hydroxy. Similar results are obtained'when the diphenyldichlorosilane is replaced by an equimolar amount of one of various other diorganodichlorosilanes as described by structure Ill, and when the derivativeof anthraquinone is replaced by an equimolar amount of the 1,4 or 1 ,5 or 1,8 derivative of anthraquinone where n=1,2,3,or4.. I

' EXAMPLE6 l,4 Bis[2-(2 hydroxyethoxy)ethylamino] anthraquinone (19.9 g, 0.0482 mole) and diphenyldiethoxysilane (13.1 g, 0.0482 mole)are placed in a 500-ml three-necked flask equipped with anitrogen inlet, a mechanical stirrer, a vacuum source, and an outlet to a collection flask. The reaction mixture is put under a nitrogen atmosphere, and the reaction flask is gradually heated to 240 C. over the period of 1 hour.

The system is evacuated with a water aspirator for 1 hour during which time the reaction flask is kept at 240 C. At the end of this period, the vacuum source is switched to a vacuum pump (0.5-1.0 mm of Hg.), and

the evacuation by vacuum pump and heating at 240 C.

are maintained forx hour. Stirring is maintained throughout the entire preparations. The polymers number-average molecular weight is 2,000 i 25 percent. A filrn cast from chloroform appears blue in color. The polymer conforms to structure I wherein n is 2, R is phenyl, Q is as shown in structure Ila, and R, is

' hydrogen. Similar results are obtained when diphenyldiethoxysilane is replaced by an equimolar amount of one of the other diorganodiethoxysilanes as described by structure Ill, and when the derivative of anthraquinone is replaced by an equimolar amount of the 1,4 or 1,5 or 1,8 derivative of anthraquinone, where n=1 2, 3, or 4.

As mentioned above,

. .yldianilinosilaneof Example 3;

to the inventionareuseful in photore-sist systems in order tozbe better. able to'observethe formation of-the resist images.- The invention provides organic solvent soluble polymeric dyes which, when used in a photore-.

sist system, suchas a positive-working system based on o-quhonediazides, impart red, green or blue'colorde- EXAMPLE] I A positive-working resist formulation containing the, polymeric dye of Example 3 is prepared as follows:

ation is prepared f A. A light-sensitive coating formul containing thefollbwing materials; g

33.0 g ofa copolymer of p-aminostyrene-styrene sulfonamide of naphthoquinone-'( l,2)-diazide-('2 the polymeric dyes according claimed'with pumice land immersionin 5 percent hydrochloric acid for 30 secondsat room temperature.

' The plates are dried for 30 minutes atroom tempera- 1 sulfochloride (Prepared as described in Example 5 I of Rauner. et-al. U.S. Pat. Application Ser. No.

684,636, filed Nov. 21, 1967.) 240.0 g cresol-formaldehyde resin 930 g methyl cellosolve acetate 70 g 4-butyrolactone 8.0 g ofthe condensation product of 1,4-bis(2-' I hydroxyethylamino)anthraquinone and diphen'- B. A sheet'of.copper is cleaned by scrubbing with fine pumice and-water',-rinsed with distilled water, and

the excess water removed with an: air jet. The plate'is driedfor S minutesat C. The coating formulation is whirl coated at 80 rpmfor 1% hour onto the, copper plate and the element is prebaked 'at 75 C. for 30 minutes. The plate is exposed iniagewise to acarbon are for 5 minutes with an intensity of 2,000 foot-candles. The, exposed plate is, tray developed with agitation for 3 minutes in l.7 percent' aqueous sodium hydroxide solution. A high gloss, greenish blue image is obtained; however, with -;subsequent handling in room light, the yellow colored component that is present dueto the light-sensitive v polymer is bleached and anexcellent cyan colored image of highvisual contrast is obtained.

' EXAMPLES Resist coatings are made as in Example 7 but without the polymeric dye andresult in a yellow colored image.

yellow safelight such as is often used in the trade. Further, on exposure to room light for a brief period of a time (an hour or so), the yellow image fades and the contrast is'greatly reduced thus making it difficult to recognize the resist image.

' EXAMPLE 9 A polymer dye (0.56 g) prepared by the melt copolymerization of .diphenyldianilinosilane with 1,4-

.bis(2-hydroxyethy lamino)anthraquinone (Example 3) is coated on copper plates that have previously been- However, such an image is not readily visible under a I "ture plus an additional 30 minutes at 50 C. The coatings are exposed imagewise for 10 minutes with an intensity of 2,000. foot-candles. -The plates are developed for 2 minutes in a mixture of xylene and.

methyl cellosol ve acetate. A dark, brown image is ob-. tained. 1

EXAMPLE 10' A positive-working formulation is prepared' as follows: w i

4.0 g of the copolymer of p-aminostyrene-styrene sulfonamide, of naphthoquinon e(1,2)-diazode- (2)- 5-sulfochloride used in Example7 I 28.0 g of cresol formaldehyde resin v 0.80 g of the polymer dye of Example 3 88.0 cc of methyl Qellosolve acetate 12.0 cc of 4-butyrolactone. Theformulation is coated on apolyester transparent substrate, exposed imagewi'se, and developed-in aqueous '1.5 percent sodium hydroxide solution. A cyan colored image on a transparent substrate is obtained.

EXAMPLE 11 'A positive working resist formulation containing the 230 g'cresolformaldehyde resin (Alnovol-429K'" sold by American HoechstCorporation) 1 l0 Phenolic resin 5254 (a 100 percent-Phenolic non-heat hardening .oil soluble resin sold by Union Carbide'Co.) v

4.0 g chlorinated biphenyl :(Arochlor 5460? sold .PLMQQE BEQQQJ 2.0 g Malonic acid 8.0 g the polymer of Example 4 I 930 cc Methyl cellosolve acetate cc 4-Butyrolactone- A coating is prepared with theabove-forrnulation as in Example v6 and exposed for 4 minutesto a carbon arc with an intensity of 2,000 foot-candles. The plate is treated with 1.2 percent aqueous sodium hydroxide with slight swabbing. A good glossy image is obtained which is greenish in color, but with subsequent nonimage exposure a good cyan image is obtained.

EXAMPLEYIZ A positive-working resist formulation containing a polymeric dye of Example 5; is prepared with the following materials;

' 4.0 g of the positive-working polymeric naphthoquinonediazide used in Example 7 23.0 g Phenolic resin (*Alnovol 429K; a cresolformaldehyde resin sold by American Hoechst l 1.0 g Phenolic resin 5254 (a percent phenolic non-heat hardening oil soluble resin sold by Union Carbide Co.)

0.2 g Phenoxy resin PHD (a high molecular weight copolymer of epichlorohydrin and bisphenol A sold by Union Carbide Co.)

t ained which is greenish in color, but with subsequent uniform exposure a good cyan image is obtained.

' EXAMPLE 13 A positive-working resist formulation containing a polymeric dye of Example 6 is prepared with the following materials:

4.0 g of a positive-working polymeric one diazide used in Example 7,

naphthoquin- 23.0 g Phenolic. resin '(Alnovol 429K, acresol-for- V maldehyde resin sold by American Hoechst Corporation) I 11.0 g Phenolic resin (5254, a 100 percent phenolic I non-heat hardening oil soluble resin sold by Union Carbide Co.) 0.4 g chlorinated biphenyl (Arochlor 5460, sold by Monsanto Chem. Co.) 0.2 g Malonic acid a 0.8 g polymer of Example 6 93.0 cc-Methyl cellosolve acetate 7.0 cc 4-Butyrolactone.

A coating is prepared as in Example 7 and exposed for 4 minutes to a carbon arc with an intensity of 2,000 foot-candles. The plate is treated with 1.1 percent aqueous sodium hydroxide. A good glossy image is obtained which is greenish in color. With subsequent uniform exposure a good cyan image is obtained.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

What is claimed is:

1. A dye copolymer of substantially equimolar amounts of a dioroganodifunctionalsilane and an anthraquinone derivative having two aliphatic hydroxy groups, said copolymer comprising repeating units havwherein n is an integer of 1 to 4; R, is a member selected from the group consisting of a lower alkyl, a lower cycloalkyl, a lower alkenyl and a lower aryl; and Q is a divalent anthraquinonylene radical selected from the group consisting of:

divalent radical having the formula:

wherein R is selected fro the group consisting of hydrogen and hydroxy.

3. A copolymer as defined in claim 1 wherein R, is

selected from the group consisting of an alkyl of one to four carbonatoms and phenyl, and R is hydrogen.

4. A copolymer as defined in claim 1 wherein n is 1,

. R, is phenyl and R is hydrogen.

5. A copolymer as defined in claim 1 wherein n is 2, R, is phenyl, and R is hydrogen.

6. A copolymer as defined in claim 2 wherein n is l, R, is phenyl and R is hydrogen;

7. A copolymer as defined in claim 2 wherein n is 2, R, is phenyl, and R, is hydrogen. 

2. A copolymer as defined in claim 1 wherein Q is a divalent radical having the formula:
 3. A copolymer as defined in claim 1 wherein R1 is selected from the group consisting of an alkyl of one to four carbon atoms and phenyl, and R2 is hydrogen.
 4. A copolymer as defined in claim 1 wherein n is 1, R1 is phenyl and R2 is hydrogen.
 5. A copolymer as defined in claim 1 wherein n is 2, R1 is phenyl, and R2 is hydrogen.
 6. A copolymer as defined in claim 2 wherein n is 1, R1 is phenyl and R2 is hydrogen.
 7. A copolymer as defined in claim 2 wherein n is 2, R1 is phenyl, and R2 is hydrogen. 